CN103562266A - Polyalkylene oxide particles and production method for same - Google Patents
Polyalkylene oxide particles and production method for same Download PDFInfo
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- CN103562266A CN103562266A CN201280026616.5A CN201280026616A CN103562266A CN 103562266 A CN103562266 A CN 103562266A CN 201280026616 A CN201280026616 A CN 201280026616A CN 103562266 A CN103562266 A CN 103562266A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/08—Saturated oxiranes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/08—Saturated oxiranes
- C08G65/10—Saturated oxiranes characterised by the catalysts used
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/08—Saturated oxiranes
- C08G65/10—Saturated oxiranes characterised by the catalysts used
- C08G65/12—Saturated oxiranes characterised by the catalysts used containing organo-metallic compounds or metal hydrides
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/2645—Metals or compounds thereof, e.g. salts
- C08G65/266—Metallic elements not covered by group C08G65/2648 - C08G65/2645, or compounds thereof
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/269—Mixed catalyst systems, i.e. containing more than one reactive component or catalysts formed in-situ
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
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Abstract
The present invention pertains to a production method for polyalkylene oxide particles, comprising a step in which alkylene oxide is polymerized in a polymerization solution including a polymerization solvent and a catalyst dispersed in said polymerization solvent, and polyalkylene oxide particles are generated. The average particle diameter of the catalyst is greater than 25 micrometer.
Description
Technical field
The present invention relates to a kind of polyalkylene oxide particle and manufacture method thereof.
Background technology
Polyalkylene oxide is owing to having water-soluble and thermoplasticity, therefore for purposes such as paper grade (stock) stick, ceramic binder, polymerization-stable auxiliary agent and pharmaceutical preparation raw materials.While polyalkylene oxide being used as to the thickening materials such as paper grade (stock) stick, with regard to the viewpoint of control viscosity, conventionally preferably there is the polyalkylene oxide of high molecular.As the manufacture method with the polyalkylene oxide of high molecular, reported to utilize to make organic zinc compound and aliphatic polyol and monohydroxy-alcohol react to obtain the method (referring to Patent Document 1) of catalyzer.
Conventional art document
Patent documentation
Patent documentation 1: Japanese kokai publication hei 5-17566 communique
Summary of the invention
The technical task that invention will solve
Yet learn, the polyalkylene oxide that the manufacture method of recording by patent documentation 1 obtains is such as when as tackifier such as paper grade (stock) sticks, and existence is difficult to the tendency dispersing or dissolving in the media such as water.
Therefore, the object of the present invention is to provide a kind of polyalkylene oxide particle and manufacture method thereof of the excellent dispersion in the media such as water.
Means for technical solution problem
The present invention relates to a kind of manufacture method of polyalkylene oxide particle, it possesses following operation (polymerization process): containing polymer solvent and be scattered in the polymer fluid of the catalyzer in this polymer solvent, making alkylene oxide polymerization and generate polyalkylene oxide particle.The median size of above-mentioned catalyzer is greater than 25 μ m.
The excellent dispersion of the polyalkylene oxide particle obtaining by above-mentioned manufacture method in the media such as water.
Preferred above-mentioned catalyzer is organic zinc catalyzer.And, the particle shape resultant of reaction of preferred above-mentioned organic zinc catalyzer for obtaining by the following method, aforesaid method comprises the operation (reaction process) that organic zinc compound is reacted with aliphatic polyol and monohydroxy-alcohol and generate particle shape resultant of reaction.
Polymer fluid contains this organic zinc catalyzer, thus can be by the molecular weight control get Geng Gao of polyalkylene oxide.
With respect to 1 mole of oxirane, in above-mentioned polymer fluid, preferably contain 0.00005 mole of above above-mentioned catalyzer.Usage quantity by catalyzer is above-mentioned scope, can suppress the decline of polymerization rate, thereby polymerization time is controlled as shorter.
The present invention also relates to a kind of polyalkylene oxide particle that can obtain by above-mentioned manufacture method.In polyalkylene oxide particle of the present invention, the ratio with the particle of the particle diameter that is less than 150 μ m is less than 40 quality %.
Invention effect
The excellent dispersion of the polyalkylene oxide particle that can obtain by manufacture method of the present invention in the media such as water.In addition, above-mentioned polyalkylene oxide particle is difficult for cohesion in the media such as water, so solvability is also excellent.
Embodiment
Below embodiments of the present invention are described.But the present invention is not limited to following embodiment.
The manufacture method of the polyalkylene oxide particle that present embodiment is related possesses following operation: containing polymer solvent and be scattered in the polymer fluid of the catalyzer in this polymer solvent, making alkylene oxide polymerization and generate polyalkylene oxide particle.
Oxirane for example can be at least a kind that is selected from oxyethane, propylene oxide, butylene oxide ring, epoxy cyclohexane, Styrene oxide 98min. and Epicholorohydrin.In these oxiranes, with regard to the solvability with respect to water of obtained polyalkylene oxide, compared with regard to high aspect, be applicable to using oxyethane or propylene oxide.These oxiranes can be distinguished separately and to use, also use capable of being combined two or more.
Polymer solvent for example can be selected from the hydrocarbon solvent of at least a kind in Skellysolve A, normal hexane, normal heptane and hexanaphthene.In these polymer solvents, with regard to industrial easy acquisition aspect and boiling point lower than the fusing point of obtained polyalkylene oxide and polyreaction after easily with regard to removal aspect, be applicable to using normal hexane or Skellysolve A.These polymer solvents can be distinguished separately and to use, also use capable of being combined two or more.
Just remove heat of polymerization and easily control with regard to the aspect of polyreaction, with respect to oxirane 100 mass parts, the usage quantity of polymer solvent is preferably 200～10000 mass parts, more preferably 400～600 mass parts.
Catalyzer in present embodiment is generally particle shape.The median size of catalyzer is greater than 25 μ m, is preferably 30～50 μ m, more preferably 35～45 μ m.When the median size of catalyzer is 25 μ m when following, exist the particle diameter of the polyalkylene oxide particle obtaining little, the tendency that the swelling in the media such as water accelerates, and exist to produce in medium and disperse bad tendency.The value of the median size of catalyzer is measured by laser diffractometry described later.
With regard to can obtaining the aspect of the polyalkylene oxide with high molecular, catalyzer is preferably organic zinc catalyzer.Organic zinc catalyzer as catalyzer is preferably the particle shape resultant of reaction that can obtain by the following method, and aforesaid method comprises the reaction process that organic zinc compound is reacted with aliphatic polyol and monohydroxy-alcohol and generate particle shape resultant of reaction.
For obtaining the organic zinc compound of organic zinc catalyzer, be for example with general formula ZnR
2the compound that (R represents any monovalent organic radical) represents.As R, cycloalkyl that can to enumerate carbonatoms and be 1～6 alkyl, phenyl and carbonatoms be 4～6 etc.Concrete example as organic zinc compound can be enumerated: the dialkyl group zinc such as zinc methide, zinc ethyl, diη-propyl zinc and di-n-butyl zinc; Phenylbenzene zinc and two cyclobutyl zinc etc.These organic zinc compounds can be distinguished separately and to use, also use capable of being combined two or more.
For the aliphatic polyol that obtains as the above-mentioned particle shape resultant of reaction of organic zinc catalyzer, it is the fatty alcohol that there are 2 above hydroxyls and there are 2 above carbonatomss.Aliphatic polyol for example can be selected from ethylene glycol, propylene glycol, 1,2-butyleneglycol, 1,3 butylene glycol, BDO, 2,3-butanediol, 1,5-PD, 2,3, in 4-penta triol, glycerine and tetramethylolmethane at least a kind.With regard to can obtaining the aspect of the polyalkylene oxide with high molecular, it is 4 aliphatic polyol that aliphatic polyol is preferably carbonatoms.Carbonatoms is that 4 aliphatic polyol for example can exemplify 1,3 butylene glycol and BDO.These aliphatic polyols can be distinguished separately and to use, also use capable of being combined two or more.
With respect to 1 mole of organic zinc compound, the usage quantity of aliphatic polyol is preferably 0.1～1.1 mole, more preferably 0.3～0.9 mole.When with respect to 1 mole of organic zinc compound and the usage quantity of aliphatic polyol while being less than 0.1 mole, exist polymerization rate extremely to decline and expend the possibility in reaction times, there is the tendency that is unfavorable for economic aspect.When with respect to 1 mole of organic zinc compound and the usage quantity of aliphatic polyol while surpassing 1.1 moles, the polyalkylene oxide particle obtaining may condense and become bulk.
For obtaining monohydroxy-alcohol as the above-mentioned particle shape resultant of reaction of organic zinc catalyzer, be the alcohol that there is 1 hydroxyl and do not there is the active hydrogen beyond the active hydrogen of hydroxyl.Monohydroxy-alcohol is such as can be primary alconols such as being selected from methyl alcohol, ethanol, 1-propyl alcohol and n-butyl alcohol; The secondary alcohol such as 2-propyl alcohol and 2-butanols; And in the tertiary alcohol such as the trimethyl carbinol at least a kind.In these alcohol, just can obtain molecular weight compared with regard to high polyalkylene oxide aspect, it is 1～6 monohydroxy-alcohol that monohydroxy-alcohol is preferably carbonatoms.The monohydroxy-alcohol that is 1～6 as carbonatoms, for example, can enumerate ethanol, propyl alcohol and butanols.These monohydroxy-alcohols can be distinguished separately and to use, also use capable of being combined two or more.
With respect to 1 mole of organic zinc compound, the usage quantity of monohydroxy-alcohol is preferably more than 1 mole, and more preferably 2～15 moles, more preferably 4～12 moles.When with respect to 1 mole of organic zinc compound and the usage quantity of monohydroxy-alcohol while being less than 1 mole exists the polyreaction of oxirane to be difficult to the tendency of carrying out swimmingly.When with respect to 1 mole of organic zinc compound and the usage quantity of monohydroxy-alcohol while surpassing 15 moles, while removing unreacted alcohol as existing as described later, removal amount increases, thereby removes elongated tendency of required time.
Monohydroxy-alcohol calculates with (mole number of the mole number/aliphatic polyol of monohydroxy-alcohol) with respect to the mol ratio of aliphatic polyol.Preferably this mol ratio is more than 2, more preferably 4～50.When above-mentioned mol ratio is less than 2, exist the polyreaction of oxirane to be difficult to the tendency of carrying out swimmingly.When above-mentioned mol ratio surpasses 50, while removing unreacted alcohol as existing as described later, remove elongated tendency of required time.Along with above-mentioned mol ratio increases, exist the median size of the catalyzer obtaining to become large tendency.
Organic zinc compound is not particularly limited with the method that aliphatic polyol and monohydroxy-alcohol react.For example can react by the following method: after (1) makes organic zinc compound react with monohydroxy-alcohol, the method that resultant is reacted with aliphatic polyol; (2) after organic zinc compound is reacted with aliphatic polyol, the method that resultant is reacted with monohydroxy-alcohol; And (3) make the method for organic zinc compound and aliphatic polyol and monohydroxy-alcohol simultaneous reactions.In these methods, with regard to viewpoint easy and simple to handle, especially suitable is the method that (3) make organic zinc compound and aliphatic polyol and monohydroxy-alcohol simultaneous reactions.
With regard to the viewpoint of reacting swimmingly, reacting conventionally containing catalyzer preparation with in the reaction solution of solvent between organic zinc compound and aliphatic polyol and monohydroxy-alcohol carried out under inert gas atmosphere.
As catalyzer, preparation can be enumerated the hydrocarbon solvents such as Skellysolve A, normal hexane, normal heptane and hexanaphthene etc. with solvent.These catalyzer preparations, with in solvent, with regard to the aspect of industrial easy acquisition, stay in grade and cheapness, are applicable to using normal hexane or normal heptane.The preparation of these catalyzer can distinguish use separately with solvents, also use capable of being combined two or more.
As rare gas element, as long as the organic zinc catalyzer obtaining is that the gas that is difficult for inactivation is not particularly limited, for example, can enumerate nitrogen, argon gas and helium.
When organic zinc compound is reacted with aliphatic polyol and monohydroxy-alcohol, preferably the mixed solution of aliphatic polyol and monohydroxy-alcohol is supplied in to the reaction solution that contains organic zinc compound and above-mentioned solvent, or aliphatic polyol and monohydroxy-alcohol are supplied in respectively to the reaction solution that contains organic zinc compound and above-mentioned solvent.In reaction system, the speed of (reaction solution) supply (interpolation) aliphatic polyol or monohydroxy-alcohol was preferably below 10g/ minute, more preferably below 2g/ minute.By feed speed, be below 10g/ minute, existence can control to tendency more among a small circle by the size-grade distribution of obtained catalyzer.And the temperature of the reaction system (reaction solution) when supplying with aliphatic polyol or monohydroxy-alcohol in reaction system is preferably 0～60 ℃.
After aliphatic polyol and monohydroxy-alcohol are supplied in reaction system, for alcohol is reacted with organic zinc compound, the temperature that also can change in reaction system is adjusted into other temperature (temperature of reaction).Temperature of reaction is generally 0～200 ℃, is preferably 20～200 ℃.Reaction times is for example 0.5～10 hour.
The reaction solution that contains organic zinc compound, aliphatic polyol and monohydroxy-alcohol preferably stirs.Stirring can be undertaken by known method.Preferred low stirring velocity.By low stirring velocity, there is the larger tendency of average particle diameter became of the catalyzer obtaining.
Above-mentioned catalyzer is prepared the dispersion liquid in the solvent of use, unreacted aliphatic polyol and monohydroxy-alcohol etc. state to be scattered in catalyzer obtains.With regard to carrying out swimmingly the viewpoint of polyreaction, preferably unreacted alcohol is removed from dispersion liquid.With regard to suppressing the viewpoint of catalyst deactivation, preferably using and in fact only contain catalyzer preparation and as the state of dispersion agent, catalyzer is supplied in to polyreaction with the dispersion liquid of solvent.
With respect to 1 mole of oxirane, polymer fluid is preferably and contains 0.00005 mole of above catalyzer, more preferably contains 0.0001～0.0006 mole.With respect to 1 mole of oxirane and the content of catalyzer while being less than 0.00005 mole, possible polymerization rate extremely declines and polymerization time is elongated.
Containing polymer solvent and be scattered in the polymer fluid of the catalyzer in this polymer solvent, the method for alkylene oxide polymerization is not particularly limited.For example can in polymerization container, add polymer solvent and catalyzer, and then add oxirane and prepare polymer fluid, under inert gas environment, one side stirs polymer fluid and simultaneously makes alkylene oxide polymerization.Just improve the aspect of polyreaction efficiency and prevent that obtained polyalkylene oxide particle from becoming with regard to block aspect, polyreaction normally one side stirs polymer fluid and simultaneously carries out.
As long as the above-mentioned rare gas element using in polyreaction, for to make catalyzer be difficult for the gas of inactivation, is not particularly limited.For example can enumerate nitrogen, argon gas and helium.
The polymerization temperature of polyreaction (temperature of polymer fluid) is generally 5～100 ℃, is preferably 20～50 ℃.The time of polyreaction is generally 0.5～10 hour.
After polyreaction finishes, for example, to being dried by filtering the resultant taking out, obtain thus the powder of polyalkylene oxide particle.
The polyalkylene oxide particle so obtaining comprises the different a plurality of particles (primary particle) of particle diameter conventionally.Particularly the polyalkylene oxide particle of present embodiment has a feature in the following areas: the content of the particle that particle diameter is little is few.In this polyalkylene oxide particle, with regard to the dispersed and deliquescent viewpoint in the media such as water, the ratio that is preferably the particle with the particle diameter that is less than 150 μ m is less than 40 quality %, is more preferably less than 30 quality %, more preferably be less than 20 quality %, be especially preferably and be less than 10 quality %.There is no particular restriction to have the lower limit of ratio of particle of the particle diameter that is less than 150 μ m, also can be 0 quality %.Having in polyalkylene oxide particle is less than the value (size-grade distribution) of above-mentioned mass percent of particle of the particle diameter of 150 μ m and can measures by aftermentioned mesh through type staging.The primary particle size that is equivalent to polyalkylene oxide particle in the most situation of above-mentioned particle diameter.
In the manufacturing process of the polyalkylene oxide particle of present embodiment, use the catalyzer with specific median size, in the size-grade distribution of obtained polyalkylene oxide particle, the ratio of small-particle reduces thus.Therefore, dispersiveness and the solvability of polyalkylene oxide particle in the media such as water improves.
embodiment
Below, according to Production Example, embodiment and comparative example, the present invention is described in detail.Yet the present invention is not only defined in this embodiment.
[evaluation method]
In accordance with the following methods the polyalkylene oxide particle obtaining in the catalyzer obtaining in Production Example and embodiment is evaluated.
(1) median size of catalyzer
The median size of catalyzer is measured by following laser diffractometry.
Use hexane as carrier, make catalyst pulp.Make above-mentioned catalyst pulp in laser diffraction formula particle size distribution device (company of Shimadzu Seisakusho Ltd. system, model: circulate SALD-7100), and measure the median size of catalyzer.
(2) size-grade distribution of polyalkylene oxide particle and mass median diameter
The size-grade distribution of polyalkylene oxide particle and mass median diameter are measured and are calculated by following mesh through type staging.
Polyalkylene oxide particle 100g and amorphous silica (Tokuyama Corp's system, the Tokuseal NP) 2g as lubricant are mixed.
As JIS Z8801-1 standard sieve, the sieve that the sieve that aperture is the sieve of 500 μ m, sieve that aperture is 300 μ m, aperture is 250 μ m, sieve that aperture is 180 μ m, sieve that aperture is 150 μ m, sieve that aperture is 106 μ m and aperture are 75 μ m sequentially coincides with and accepts on ware from top to bottom.
In being the sieve of 500 μ m, the aperture that is disposed at the superiors puts into the mixture of polyalkylene oxide particle and amorphous silica.Use rotator shaker to make sieve vibration 20 minutes, thus by mixture classification.
After classification, measure the quality of polyalkylene oxide particle residual on each sieve, calculate each quality with respect to the mass percent of total amount.From the large sieve in aperture, mass percent is sequentially added up, on logarithmic probability paper by the aperture of sieve and the relation mapping that residues in the aggregate-value (accumulative total mass percent) of the mass percent of the polyalkylene oxide particle on sieve.With straight line, the figure that done on paper is linked, the value in the aperture of the sieve when accumulative total mass percent is 50 quality % is as the mass median diameter of polyalkylene oxide particle.
In addition, calculating and residuing in sieve, the aperture that aperture is 106 μ m is the sieve of 75 μ m and the aggregate value of accepting the mass percent of the polyalkylene oxide particle on ware, as the mass percent with the particle of the particle diameter that is less than 150 μ m.
(3) dispersiveness of polyalkylene oxide particle in water
In the beaker that is 1000mL at volume, add ion exchanged water 500g, the temperature of ion exchanged water is adjusted into 25 ℃.For the ion exchanged water in beaker, one side use possesses 2 upright blade type paddles (wing footpath: stirrer 80mm) stirs with the rotating speed of 250rpm, the disposable input polyalkylene oxide particle 2.5g of one side.Stir after 10 seconds, stop stirring the polyalkylene oxide dispersion of particles state in visual observations beaker.Dispersed according to following benchmark evaluation.In following benchmark, so-called " large aggregate " refers to the thick aggregate of the degree that range estimation can be confirmed.
A: the number of large aggregate is 0 (nothing)
B: the number of large aggregate is 1～2
C: the number of large aggregate is 3～4
D: the number of large aggregate is more than 5
[Production Example 1: catalyst A]
Preparation internal diameter is the flask that 80mm, volume are 500mL, and this flask is provided with reflux exchanger, dropping funnel, nitrogen ingress pipe and as the agitating wing that wing footpath is 4 (45 degree tilt) paddles of 53mm that has of stirrer.
With nitrogen by after the air displacement in flask, (Sumitomo Chemical limited-liability company manufactures in this flask, to add normal hexane, high-purity technical is used) 56.3g and (the Nippon Oil(Nippon Mitsubishi Oil) limited-liability company manufacture of high boiling aliphatic hydrocarbon, trade(brand)name: No. 0 solvent) 9.9g, and then add zinc ethyl (Japanese aluminum alkyls limited-liability company manufacture) 9.9g(80 mmole).Reaction solution in flask is cooled to 10 ℃, and the front end circumferential speed of take stirs as 0.97m/ second (mixing speed is 350rpm).
Then, use dropping funnel, with the interpolation speed of 0.5g/ minute by BDO 6.5g(72 mmole) with ethanol 29.0g(629 mmole) the total amount of mixed solution be added in above-mentioned flask.After adding and finishing, will in flask, be warming up to 30 ℃, make zinc ethyl and BDO and ethanol synthesis 1 hour, be then warming up to 50 ℃ and carry out reacting for 1 hour.
By flask in be warming up to 140 ℃, unreacted alcohol and normal hexane in the lump distilled be removed to reaction system outside thereafter.After cooling, with normal hexane 400ml, by the reaction solution dilution in flask, obtain the dispersion liquid 302g of the organic zinc catalyzer (catalyst A) that contains 3 quality %.The measurement result of the median size of obtained catalyst A is shown in Table 1.
[Production Example 2: catalyst B]
Nose circle roll surface speed is changed to 0.55m/ second (mixing speed is 200rpm) by 0.97m/ second (mixing speed is 350rpm), in addition, carry out the operation identical with Production Example 1, obtain the dispersion liquid 302g of the organic zinc catalyzer (catalyst B) that contains 3 quality %.The measurement result of the median size of obtained catalyst B is shown in Table 1.
[Production Example 3: catalyzer C]
Nose circle roll surface speed is changed to 1.94m/ second (mixing speed is 700rpm) by 0.97m/ second (mixing speed is 350rpm), in addition, carry out the operation identical with Production Example 1, obtain the dispersion liquid 302g of the organic zinc catalyzer (catalyzer C) that contains 3 quality %.The measurement result of the median size of obtained catalyzer C is shown in to table 1.
[Production Example 4: catalyzer D]
By the usage quantity of BDO by 6.5g(72 mmole) change to 2.2g(24 mmole), in addition, carry out the operation identical with Production Example 2, obtain the dispersion liquid 302g of the organic zinc catalyzer (catalyzer D) that contains 3 quality %.The measurement result of the median size of obtained catalyzer D is shown in to table 1.
[Production Example 5: catalyzer E]
By the usage quantity of ethanol by 29.0g(629 mmole) change to 17.6g(382 mmole), in addition, carry out the operation identical with Production Example 1, obtain the dispersion liquid 302g of the organic zinc catalyzer (catalyzer E) that contains 3 quality %.The measurement result of the median size of obtained catalyzer E is shown in to table 1.
[table 1]
In table 1, so-called alcohol ratio, represents that monohydroxy-alcohol (ethanol) is with respect to the mol ratio of aliphatic polyol (BDO).So-called interpolation speed, supply (interpolation) speed of the mixed solution of aliphatic polyol and monohydroxy-alcohol is supplied with in expression (in flask) in system.Temperature in so-called system, the temperature of (reaction solution) in the system while representing to supply with the mixed solution of aliphatic polyol and monohydroxy-alcohol in system.
[embodiment 1]
Preparation internal diameter is the pressure-resistant reaction vessel that 94mm, volume are 1L, and this pressure-resistant reaction vessel is provided with dropping funnel, nitrogen ingress pipe and has the agitating wing that wing footpath is the anchor type paddle of 47mm.
With nitrogen by after the air displacement in pressure-resistant reaction vessel, (Sumitomo Chemical limited-liability company manufactures in this reaction vessel, to add polymer solvent normal hexane, high-purity technical is used) 345g, and then under agitation add in Production Example 1 the dispersion liquid 3.1g of the catalyst A obtaining, make it dispersed, prepare polymer fluid.
Then, in polymer fluid, add oxyethane 84g(1.91 mole)., polymer fluid be warming up to 30 ℃, make ethylene oxide polymerization 6 hours thereafter.
After polyreaction finishes, separated from normal hexane by filtering resultant, at 40 ℃, drying under reduced pressure is 5 hours, obtains thus polyethylene oxide particle 80.5g.The productive rate of the polyethylene oxide particle obtaining is 99.3 quality % with respect to oxyethane.Obtained polyethylene oxide particle is carried out to mass median diameter and the dispersed evaluation in water.Evaluation result is shown in table 2 and table 3.
[embodiment 2]
The dispersion liquid of catalyst A is changed to the dispersion liquid of catalyst B, in addition, obtain similarly to Example 1 polyethylene oxide particle 80.7g.The productive rate of the polyethylene oxide particle obtaining is 99.6 quality % with respect to oxyethane.Obtained polyethylene oxide particle is carried out to mass median diameter and the dispersed evaluation in water.Evaluation result is shown in table 2 and table 3.
[embodiment 3]
The dispersion liquid of catalyst A is changed to the dispersion liquid of catalyzer C, in addition, obtain similarly to Example 1 polyethylene oxide particle 80.3g.The productive rate of the polyethylene oxide particle obtaining is 99.1 quality % with respect to oxyethane.Obtained polyethylene oxide particle is carried out to mass median diameter and the dispersed evaluation in water.Evaluation result is shown in table 2 and table 3.
[embodiment 4]
The dispersion liquid of catalyst A is changed to the dispersion liquid of catalyzer D, in addition, obtain similarly to Example 1 polyethylene oxide particle 80.3g.The productive rate of the polyethylene oxide particle obtaining is 99.1 quality % with respect to oxyethane.Obtained polyethylene oxide particle is carried out to mass median diameter and the dispersed evaluation in water.Evaluation result is shown in table 2 and table 3.
[comparative example 1]
The dispersion liquid of catalyst A is changed to the dispersion liquid of catalyzer E, in addition, obtain similarly to Example 1 polyethylene oxide particle 80.4g.The productive rate of the polyethylene oxide particle obtaining is 99.3 quality % with respect to oxyethane.Obtained polyethylene oxide particle is carried out to mass median diameter and the dispersed evaluation in water.Evaluation result is shown in table 2 and table 3.
[table 2]
[table 3]
| ? | Catalyst type | Dispersiveness in water |
| Embodiment 1 | Catalyst A | A |
| Embodiment 2 | Catalyst B | A |
| Embodiment 3 | Catalyzer C | A |
| Embodiment 4 | Catalyzer D | A |
| Comparative example 1 | Catalyzer E | D |
By table 2, learnt, about the polyalkylene oxide particle obtaining in embodiment, the ratio of small-particle is few, and mass median diameter appropriateness is large.In addition, by table 3, learnt the excellent dispersion of the polyalkylene oxide particle obtaining in embodiment in water.
Claims (5)
1. a manufacture method for polyalkylene oxide particle, it possesses following operation:
Containing polymer solvent and be scattered in the polymer fluid of the catalyzer in this polymer solvent, making alkylene oxide polymerization and generate polyalkylene oxide particle,
The median size of described catalyzer is greater than 25 μ m.
2. manufacture method according to claim 1, wherein,
Described catalyzer is organic zinc catalyzer.
3. manufacture method according to claim 2, wherein,
The particle shape resultant of reaction of described organic zinc catalyzer for obtaining by the following method, described method comprises the operation that organic zinc compound is reacted with aliphatic polyol and monohydroxy-alcohol and generate particle shape resultant of reaction.
4. according to the manufacture method described in any one in claims 1 to 3, wherein,
With respect to 1 mole of described oxirane, described polymer fluid contains 0.00005 mole of above described catalyzer.
5. a polyalkylene oxide particle, wherein,
The ratio with the particle of the particle diameter that is less than 150 μ m is less than 40 quality %, and can obtain by the manufacture method described in any one in claim 1 to 4.
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| CN105722889B (en) * | 2013-11-22 | 2016-12-07 | 陶氏环球技术有限责任公司 | Zinc catalyst/additive system for epoxide monomer polymerization |
| KR102254691B1 (en) | 2014-03-31 | 2021-05-21 | 스미토모 세이카 가부시키가이샤 | Alkylene oxide polymer production method |
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| KR101907233B1 (en) | 2018-10-11 |
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